Beta-amido vinyl phosphates and their method of preparation

ABSTRACT

B-AMIDOVINYL THIOPHOSPHATES OF THE FORMULA   R2-CO-N(-R1)-C(-R3)=C(-R4)-S-P(=Z)(-O-R)2   IN WHICH R IS A HYDROCARBYL RADICAL, R1 IS A SATURATED ALIPHATIC, CYCLOALIPHATIC OR ARYL RADICAL, R2, R3, AND R4 ARE HYDROGEN, SATURATED ALIPHATIC, CYCLOALIPHATIC OR ARYL RADICAL, WITH THE PROVISO THAT R1 AND R2 MAY BE JOINED TO FORM AN ALKYLENE RADICAL AND Z IS OXYGEN OR SULFUR. COMPOUNDS OF THIS CLASS ARE INSECTICIDAL AND MAY BE MADE BY REACTING AN APPROPRIATE N-VINYL AMIDE WITH A PHOSPHORANE SULFENYL HALIDE.

United States Patent O 3,660,429 fl-AMIDO VINYL PHOSPHATES AND THEIRMETHOD OF PREPARATION Melancthon S. Brown, Berkeley, Calif., ,assignorto Chevron Research Company, San Francisco, Calif.

N Drawing. Original application June 7, 1967, Ser. No. 644,063, nowPatent No. 3,527,848. Divided and this application Nov. 10, 1969, Ser.No. 875,494

Int. Cl. C07d 27/08 US. Cl. 260--326.5 A 7 Claims ABSTRACT OF THEDISCLOSURE p-Amidovinyl thiophosphates of the formula 0 R R z R -ii-N-i=d-Si*(0lt in which R is a hydrocarbyl radical, R is a saturatedaliphatic, cycloaliphatic or aryl radical, R R and R are hydrogen,saturated aliphatic, cycloaliphatic or aryl radical, with the provisothat R and R may be joined to form an alkylene radical and Z is oxygenor sulfur. Compounds of this class are insecticidal and may be made byreacting an appropriate N-vinyl amide with a phosphorane sulfenylhalide.

CROSS REFERENCES TO RELATED APPLICATIONS This application is a divisionof co-pending application Ser. No. 644,063, filed June 7, 1967, now US.Pat. No. 3,527,848.

FIELD OF INVENTION This invention is directed to novel B-amido vinylphosphates and their preparation from N-vinyl amides and phosphoranesulfenyl halides.

DESCRIPTION OF INVENTION The novel phosphates of this invention areB-amidovinyl thiophosphates and dithiophosphates in Which the on carbonatom of the vinyl group is bound to the sulfur atom bonded singly tophosphorus, the nitrogen atom of the amide radical is substituted by asaturated aliphatic, cycloaliphatic or aryl group and the total numberof carbon atoms in the amido radical is less than about 20.

These compounds may be made by reacting a phosphorane sulfenyl halide inwhich the halogen has an atomic number of 17 to 35, i.e., chlorine andbromine, with an N-vinyl amide in which the nitrogen is substituted witha saturated aliphatic, cycloaliphatic or aryl radical in addition to thevinyl radical and the total number of carbon atoms of the amide,including the vinyl radical, is less than about 22, in an inert solvent.This reaction is surprising in that sulfenyl halides conventionallyreact with olefinic nnsaturation to give a saturated addition product.

Preferred B-amidovinyl thiophosphates of this invention are representedby the general formula:

in which R is a hydrocarbyl radical of 1 to about 15 carbon atoms, Z isa chalcogen atom of atomic number '8 to "16, i.e., O or S, R is asaturated aliphatic, cycloaliphatic or aryl radical containing 1 toabout 15 carbon atoms and R R and R are individually hydrogen, asaturated aliphatic, cycloaliphatic or aryl radical having 1 to about 15carbon atoms, with the proviso that R and R may be joined to form analkylene radical of 2 to about 6 carbon Patented May 2, 1972 ice(ROM-P-SX wherein R and Z are as previously defined and X is halogenhaving an atomic number from 17 to 35, with an N- vinyl amide of thegeneral formula wherein R R R and R are as previously defined.

Examples of the specific radicals which R in the above iormulas mayrepresent are aliphatic hydrocarbyl groups such as methyl, ethyl,isopropyl, sec. butyl, hexyl and vinyl, cycloaliphatic groups such ascyclobutyl, cyclohexyl and cyclooctyl, and aryl groups such as phenyl,tolyl and benzyl. Illustrative of radicals which R R R and R mayrepresent are methyl, ethyl, chloroethyl, isopropyl, hexyl, octyl,cyclobutyl, cyclohexyl, phenyl, chlorophenyl, nitrophenyl, tolyl andxylyl. In the instance where R and R are joined they may be ethylene,propylene, butylene and the like.

Specific examples of B-amidovinyl thiophosphates represented by Formula1 are 0,0-dimethyl-/3-(N-methylformamido)vinyl thiophosphate,

0,0-dimethyl-}8-(N-isopropylacetamido)vinyl dithiophosphate,

O-ethyl-O-methyl-B- (N-2-chloroethylpropionamido vinyl thiophosphate,

O,Ol-1diethyl-,8-(N-butylpropionamido)vinyl dithiophosp ate,0,0-dibutyl-,8-(N-methylvaleramido)vinyl thiophosphate,0,0l;dicyclohexyl-B-(N-hexylacetarnido)vinyl thiophosp ate,0,0};diphenyl-fl-(N-methylacetamido)vinyl thiophosp ate,0,0};diisopropyl-fl-(N-ethylbenzamido)vinyl thiophosp ate,0,0};diethyl-fi- (N-ethylcyclohexanamido) vinyl thiophosp ate,0,0-dibutyl-fi-(N-cyclohexyl-2-naphthamido)vinyl thiophosphate,0,0-dimethyl-a-methyl-B-(N-methylacetamido)vinyl thiophosphate,0,0-dimethyl-a-butyl-fi-(N-methylbenzamido)vinyl thim phosphate,0,0-diethyl-a-cyclohexyl-fl-(N-phenylacetamido)rvinyl dithiophosphate,0,0-diisopropyl-u-phenyl-fi-ethyl-p-(N-ethylacetamido) vinylthiophosphate and 0,0-dimethyl-u-ethyl-fl-phenyl-fi-(N-ethylacetamido)vinyl thiophosphate, N-B-QO-diphenylphosphorylthiovinyl-Z-pyrrolidone,N-p-O, O-dibutylphosphorylthiovinyl-Q-pyrrolidone and'N-ei-0,0-dimethylthionophosphorylthiovinyl-Z-pyrrol- 1 one.

The reaction of this invention is carried out in inert solvents such asethyl ether, dioxane, benzene, chloroform and methylene dichloride. Thereaction temperature will normally be in the range of -20 to 50 C.,preferably 0 to 25 C. The concentration of reactants is not critical;proportions approximating stoichiometric amounts will usually beemployed. While it is desirable to run the reaction in the presence ofan HCl acceptor such as a tertiary amine, e.g. trialkylamine, alkalimetal carbonate, water, etc., an HCl acceptor is not necessary. Ingeneral, the fl-amidovinyl thiophosphates are oils and may be separatedfrom the reaction mixture by filtering off hydrochloride precipitates ofthe HCl acceptors and removing the solvent from the filtrate in vacuo.

EXAMPLES The following examples further illustrate the novel 19-amidovinylthiophasphosphates of the invention and their method ofpreparation. These examples are intended only to illustrate thisinvention and are in no way meant to limit it. Unless otherwiseindicated, percentages are by weight.

EXAMPLE 1 Fifteen grams of N-vinyl-N-methylacetamide in 200 ml. ethylether were charged to a flask immersed in an ice bath. 35 g. ofdiisopropylphosphorane sulfenyl chloride in 50 ml. ethyl ether wereadded slowly to the flask over about an hour. This mixture was stirredfor one hour after adding the sulfenyl chloride. g. of triethylaminewere then added and the mixture was allowed to warm to ambienttemperature and stand overnight. It was then filtered and washed withethyl ether. The ether was removed under vacuum and the oily residue wasdissolved in 200 ml. chloroform and washed three times with water. Itwas then dried, the chloroform was removed under vacuum and it was driedagain at 80 C., 0.2 mm. Hg for 3 hours. 38.2 g. of0,0-diisopropyl-;8-(N-methylacetamido)vinyl thiophosphate was recovered.Its S analysis was: calculated 10.83%; found 10.85%.

EXAMPLE 2 Fifteen grams of N-vinylpyrrolidone in 200 ml. ethyl etherwere placed in a flask immersed in an ice bath. 31 g. ofdiisopropylphosphorane sulfenyl chloride in 50 ml. ethyl ether wereadded slowly to the flask. The combined mixture was stirred for 1 hourafter the sulfenyl chloride had been added. 15 g. of triethylamine werethen added to the mixture and the flask was allowed to warm to ambienttemperature and stand overnight. The mixture was then filtered andwashed with ethyl ether. The ether was removed from the filtrate undervacuum leaving an oily residue. The residue was dissolved in chloroformand washed three times with cold water. It was dried, the chloroformremoved under vacuum and dried again at 80 C., 0.2 mm. Hg for 3 hours.36.3 g. of N-B-QO-diisopropylphosphorylthiovinyl-Z-pyrrolidone wasrecovered. Its S analysis was: calculated 10.41%; found 10.12%.

Other fl-amido vinyl thiophosphates included in this invention wereprepared using the general methods described in Examples 1 and 2. Thesecompounds and their analyses appear in Table 'I.

p-Amidovinylthiophosphates of this invention have exhibited insecticidaland acaricidal activity. Organisms which were significantly controlledby insecticidal or acaracidal amounts of these compounds of thisinvention included mites, flies, aphids, cockroaches and dockbeetles.

In using these compounds as insecticides it is expected that they may beformulated in insecticidal 'or acaracidal amounts with various inertdiluents, other biologically active compounds, stickers, surface activeagents and the like. In this form they may be applied in toxic amountsto the insects, acarids, or their environments by methods and meansestablished in the art.

I claim:

1. Method for preparing compounds of the general formula in which Z is achalcogen atom of atomic number 8 to 16, R is alkyl of 1 to 6 carbonatoms, cycloalkyl of 4 to 8 carbon atoms, phenyl, tolyl or benzyl, R andR are joined to form an alkylene radical of 2 to 3 carbon atoms and Rand R are individually hydrogen, alkyl of 1 to 8 carbon atoms,cycloalkyl of 4 to 6 carbon atoms or phenyl, which comprises reacting acompound of the formula wherein X is halogen of atomic number 17 to 35and R and Z are as previously defined, with a compound of the formula er R dNC=( JH wherein R R R and R are as previously defined, in thepresence of an inert solvent and an HX acceptor wherein X is as definedpreviously.

2. Method of claim 1 wherein the reaction is carried out from 20 to 50C.

3. Method of claim 1 wherein Z is oxygen, R is alkyl of l to 6 carbonatoms, cyclohexyl or phenyl, R and R are joined to form an alkyleneradical having 2 to 3 carlbOl'l atoms and R and R are hydrogen.

4. Method of claim 1 wherein Z is oxygen, -R is methyl, ethyl orisopropyl, X is chlorine, R and R are joined to form an ethylene radicaland R and R are hydrogen.

5. Compound of the formula 0 Ila R4 Z R iiI Ic= i1-s P-(om,

wherein Z is a chalcogen atom of atomic number 8 to 16, R is alkyl of 1to 6 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, phenyl, tolyl, orbenzyl, R and R are joined to form an alkylene radical of 2 to 3 carbonatoms and R and R are individually hydrogen, alkyl of 1 to 8 carbonatoms, cycloalkyl of 4 to 6 carbon atoms or phenyl.

6. Compound of claim 5 wherein Z is oxygen, R is alkyl of 1 to 6 carbonatoms, cyclohexyl or phenyl, R and R are joined to form an alkyleneradical of 2 to 3 carbon atoms and R and R are hydrogen.

7. Compound of claim 5 wherein Z is oxygen, R is methyl, ethyl orisopropyl, X is chlorine, R and R are joined to form an ethylene radicaland R and R are hydrogen.

References Cited UNITED STATES PATENTS 3,316,145 4/1967 Haubein 260326.5X

ALEX MAZEL, Primary Examiner J. A. NARCAVAGE, Assistant Examiner US. Cl.X.R. 260-29585, 945; 424200 age warm STATES PATENT @FHEE @ERHMQA'EE @h@QRREQTWN Patent No. 3,660,1429 Dated May 2, 1972 Inventor(s)Melanc'thon 8.. Brown It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

C019 1, line 62., last part of formula," S-(OR) should read C010 3, line13, "amidovinylthiophaephosphares" should read--amidovihylrhiophosphares-.

Colo 3, Table I, N, Found rth line "5097" should read Signed and sealedthis 5th day of September 1972.a

(SEAL) Arrest:

EDWARD MQFLETGIER JRW ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

